Moldable resin composition based on copolysters elastomers

ABSTRACT

Blow-moldable resin compositions based on polyether ester elastomers or block copolymers n which rubber-like polyether soft segments and plastic-like hard segments are alternately linked to one another.

BACKGROUND OF THE INVENTION

[0001] 1. Field of the Invention

[0002] The invention relates to moldable resin compositions and moldedarticles obtained therefrom.

[0003] The invention relates in particular to blow moldable resincompositions based on polyether ester elastomers or block copolymers inwhich rubber like polyether soft segments and plastic like hard segmentsare alternately linked to one another.

[0004] 2. Description of the Related Art

[0005] The blow molding of polyesters in particular polyether esterelastomers is known, but remains problematic especially for the blowmolding of very long parts which requires specific rheologicalproperties, in particular a closely controlled high melt strength toavoid unwanted sagging.

[0006] U.S. Pat. No. 4,010,222 reports that the addition of a copolymercontaining polymerized ethylene units and polymerized carboxylic acidunits to a copolyester elastomer improves its processing by blowmolding.

[0007] U.S. Pat. No. 4,912,167 describes a blow moldable composition ofa polyester such as polybutylene terephthalate (PBT), polyethyleneterephthalate (PET) or a PBT/PET blend, an epoxide polymer and a sourceof catalytic ions.

[0008] U.S. Pat. No. 5,128,404 describes a blow moldable compositioncontaining polybutylene terephthalate, an ethylene copolymer containingepoxide groups and an ionomer obtained by partially neutralizing withNa⁺ of K⁺ the carboxyl groups of an ethylene copolymer containing(meth)acrylic acid.

[0009] U.S. Pat. No. 5,523,135 describes the problems of blow moldingthermoplastic polyester resins, and reports an improvement for acombination of a thermoplastic polyester resin, typically, PBT, with astyrenic copolymer. In Comparative Example 12 it reports that blowmolding was impossible when the PBT was replaced with a PBT-containingpolyester ether elastomer.

[0010] EP-A-0,577,508 aimed to improve the blow moldability of polyetherester elastomers (block copolymers) which hitherto were not consideredsuitable for blow molding, by mixing them with an epoxy compound and aphenol alkali metal salt.

[0011] Canadian Patent Application 2,039,132 proposed a generalimprovement in polyether ester elastomers (block copolymers) by mixingthem with an aromatic thermoplastic polyester, like PBT, PET or blendsthereof, a rubbery interpolymer and optionally a mineral filler.

[0012] Whereas certain polyether ester elastomer formulations have beensuccessfully used for blow molding, it still remains problematic toprovide a blow moldable resin composition based on polyether ester resinthat has a high parison stability, with little tendency to sag, for theblow molding of very long parts, especially for sequential co-extrusionor 3-D parison manipulation techniques.

SUMMARY OF THE INVENTION

[0013] According to the invention a moldable resin composition withimproved properties for blow molding comprises the following components(A)-(F).

[0014] (A) A blend of two polyether ester elastomers (A1) and (A2), (A1)with a hardness in the range 45-72 Shore D, in an amount 70-95 wt. % ofthe blend, and (A2) with a hardness in the range 25-40 Shore D, in anamount 5-30 wt. % of the blend.

[0015] (B) A copolymer comprising from 94 to 50 wt. % of ethylene, from5 to 35 wt. % of at least one alkyl or cycloalkyl acrylate ormethacrylate, in which the alkyl or cycloalkyl group has from 2 to 10carbon atoms, and from 1 to 15 wt. % of at least one unsaturatedepoxide.

[0016] At least one of (C) and (D), where (C) is a copolymer comprisingfrom 88 to 60 wt. % of ethylene, from 11.5 to 40 wt. % of at least onealkyl or cycloalkyl acrylate or methacrylate, in which the alkyl orcycloalkyl group has from 2 to 10 carbon atoms, and from 0.5 to 6 wt. %of at least one anhydride of an unsaturated dicarboxylic acid; and (D)is at least one rubbery polymer that can be finely dispersed into thecomposition by extrusion.

[0017] (E) A calcium compound capable of reacting with acid end-groupsof the polyether ester resins of blend (A).

[0018] (F) One or more optional additives.

[0019] In the composition according to the invention: the resin blend(A),is present in an amount of 60-90 wt. % of the composition. Copolymer(B) is present in an amount of 6-15 wt. % of the resin blend A.Copolymer (C) when present is in an amount up to 20 wt. % of thecomposition, and the rubbery polymer (D) when present is in an amount upto 20 wt. % of the composition, providing the sum of (C) and (D) is atleast 2 wt. % of the composition. The calcium compound (E) is in anamount such as to provide up to 2 wt. % elemental calcium in thecomposition. Lastly, the optional additive(s) (F) when present is/are inan amount up to 20 wt. % of the composition.

[0020] The composition according to the invention provides a highparison stability, with little tendency to sag, enabling the successfulblow molding of very long parts, which could not be achieved with priorpolyether ester elastomer formulations, at the same time combining agood surface aspect of the molded part. This composition is especiallyadvantageous for sequential co-extrusion and for 3-D parisonmanipulation techniques.

[0021] The copolyester elastomers (A) are advantageouslycopolyetheresters consisting essentially of a multiplicity of recurringlong chain ester units and short chain ester units joined head-to-tailthrough ester linkages. The long chain ester units are represented bythe formula

[0022] and the short chain ester units are represented by the formula

[0023] where G is a divalent radical remaining after removal of terminalhydroxyl groups from a poly(alkylene oxide) glycol having a molecularweight of about 400-6000 and a carbon-to-oxygen ratio of about 2.0-4.3;R is a divalent radical remaining after removal of carboxyl groups froma dicarboxylic acid having a molecular weight less than about 300 and Dis a divalent radical remaining after removal of hydroxyl groups from adiol having a molecular weight less than about 250; provided said shortchain ester units amount to about 15-95% by weight of thecopolyetherester.

[0024] Alternatively, the copolyester elastomer is a copolyester ester.

[0025] Copolyetherester elastomers and copolyester ester elastomers aredescribed for example in U.S. Pat. Nos. 4,981,908, 5,824,421 and5,731,380, the descriptions whereof are incorporated herein by way ofreference.

[0026] Polyetherester block copolymers and their preparation are alsodescribed in Encyclopedia of Polymer Science and Engineering, Volume 12,pages 76-177 (1985) and the references reported therein.

[0027] Various polyetherester block copolymers are commerciallyavailable from a number of companies under various tradenames, forexample HYTREL of E.I. du Pont de Nemours, RITEFLEX of Ticona andARNITEL of DSM.

[0028] Varying the ratio hard/soft segment and using different alkyleneoxides and molar weights of the soft segments makes it possible toobtain block copolyesters having different hardnesses, for examplebetween Shore D 25 and 80. The invention employs a blend of twopolyether ester elastomers, one with a hardness in the range 45-72 ShoreD, and the other with a hardness in the range 25-40 Shore D.

[0029] The employment of a blend of copolyester elastomers of high andlow hardnesses is critical for the invention and gives benefit for theparison aspect (less melt fracture). Moreover, the blend used in theinvention has been found to improve the surface aspect of the parisonwhen coming out of the die, leading to less surface defects in themolded part.

[0030] Using a blend of copolyester elastomers of high and lowhardnesses is not equivalent to using a single copolyester elastomer ofmedian properties. This is because the length of the soft blocks in thecopolyester elastomer tends to be longer for the softer grades, hencethe presence of even a small fraction of long soft blocks can influencethe crystallisation speed and density of entanglement retained when thematerial solidifies from the molten state.

[0031] Preferably the soft segments in the soft copolyester elastomer ispolytetramethyleneglycol (PTMEG) with a molecular weight of the order of2000, whereas the soft segment in the hard copolyester elastomer isPTMEG with a molecular weight of the order of 1000.

[0032] The relative amounts of the hard and soft copolyester elastomersare in the range 75-97 wt. %, preferably 84-94 wt. %, for the hardcopolyester elastomer and 3-25 wt. %, preferably 6-16 wt. %, for thesoft copolyester elastomer, based on the total weight of the blend.

[0033] Examples of alkyl acrylates and methacrylates that may inparticular be employed as constituents of the copolymers (B) and (C)are: methyl methacrylate, ethyl acrylate, n-butyl acrylate, isobutylacrylate and 2-ethyl-hexyl acrylate.

[0034] Examples of unsaturated epoxides that may in particular beemployed as constituents of copolymer (B) are: aliphatic glycidyl estersand ethers such as allyl glycidyl ether, vinyl glycidyl ether, glycidylmaleate and itaconate and glycidyl acrylate and methylacrylate; andalicylic glycidyl esters and ethers such as 2-cyclohexene-1-glycidylether, diglycidyl 4,5-cyclohexene-dicarboxylate, glycidyl 4-cyclohexenecarboxylate, glycidyl 5-norbornene-2-methyl-2-carboxylate and diglycidylendocdis-bicyclo(2.2.1)-5-heptene-2,3-dicarboxylate.

[0035] Examples of anhydrides of an usaturated dicarboxylic acid thatcan be employed as constituents of copolymer (C) are maleic anhydride,itaconic anhydride, citraconic anhydride and tetrahydrophthalicanhydride.

[0036] Further examples of copolymers (B) and (C) are given in U.S. Pat.Nos. 5,208,292 and 5,407,999. These patents describe thermoplasticpolyester alloys usable particularly for injection molding of articlesstrengthened against impact, comprising a saturated polyester like PETor PBT reinforced with a copolymer. This reinforcing polymer includes afirst copolymer comprising from 94 to 60 wt. % of ethylene, from 5 to 25wt. % of at least one alkyl or cycloalkyl acrylate or methacrylate, inwhich the alkyl or cycloalkyl group has from 2 to 10 carbon atoms, andfrom 1 to 15 wt. % of at least one unsaturated epoxide from 84 to 60 wt.% of ethylene; a second copolymer comprising from 15 to 34 wt. % of atleast one alkyl or cycloalkyl acrylate or methacrylate, in which thealkyl or cycloalkyl group has from 2 to 10 carbon atoms and from 1 to 6wt. % of at least one anhydride of an unsaturated dicarboxylic acid; anda compound capable of accelerating the reaction between the epoxy groupof the first copolymer and the anhydride group of the second copolymer.

[0037] Rubbery polymers which can be included in the composition of thepresent invention as component (D) include acrylate terpolymer rubbersas described in U.S. Pat. No. 5,380,785, such as those available fromGoodyear Chemical under the trademark SUNIGUM,styrene-ethylene/butylene-styrene block copolymers such as thoseavailable from Shell Chemical Company under the tradename KRATON, andmethacrylate/butadiene/styrene or butyl-acrylate/PMMA multiphasecomposite interpolymers such as those available from Rohm & Haas Counder the tradename PARALOID.

[0038] Examples of methacrylate/butadiene/styrene multiphaseinterpolymers of component (D) are those available from Atofina underthe tradename METABLEN and those available from Sonepa Polymer Additivesunder the tradename of RAJALOID.

[0039] Further examples of component (D) arestyrene-ethylene/butylene-styrene block copolymers available from TeknorApex under the tradename TEKRON and those available from Multibase underthe tradename MULTIFLEX.

[0040] Examples of the calcium compound (E) capable of reacting withacid groups of the polyether ester resins of blend (A) are: calciumoxide, calcium hydroxide, calcium salts of inorganic acids and calciumsalts of mono-, di- or polycarboxylic acids. The presence of thiscalcium compound is important because it provides enhanced viscosity ata given level of the copolymers (B) and (C), hence enables a highviscosity to be obtained while avoiding problems associated with anexcessive amount of copolymers (B) and (C). Furthermore, in order tokeep the amount of this calcium compound to a minimum value in thecomposition, it is an advantage that the weight fraction of calcium inthe calcium compound is high, which means for instance that calciumoxide or calcium hydroxide are preferred over calcium stearate.

[0041] The composition according to the invention may contain the usualadditives, for example stabilizers, ultraviolet ray-absorbers,hydrolytic stabilizers, anti-static agents, dyes or pigments, fillers,fire-retardants, lubricants, processing aids, for example releaseagents, etc, in an optional amount. These additives may for example beincluded in either component of the polyetherester block copolymerblend.

[0042] The optional additives can include a compound capable ofaccelerating the reaction between the epoxy groups present in thecopolymer (B) and the acid end-groups of the copolyester elastomer, forexample a zinc compound in an amount of up to about 1.5 wt. % of thecomposition.

[0043] The composition according to the invention is useful inparticular in blow molding processes but can also be used in othermolding processes such as extrusion molding and generally anymanufacturing method that includes the step of heating the compositionabove its melting temperature. The invention also pertains to shapedarticles made using the given composition, in particular blow moldedarticles, especially long parts.

DETAILED DESCRIPTION

[0044] The invention will be further described and compared with priorart in the following Examples and Comparative Examples.

[0045] The compositions discussed below were prepared by mixing thecomponents in the described proportions and melt blending the resultingmixtures on a 40 mm diameter twin screw extruder. Extrusion conditionswere as follows: temperature profile of the extruder: decreasing from250° C. at the hopper to 230° at the die; die temperature: 230° C.;screw speed: 300 rpm. Measured melt temperatures range from 240° C. to275° C. for the various compositions. The extrudate was pulled intostrands, cooled in a water bath and pelletized.

Description of the Measurement Methods

[0046] The melt flow rate of the materials was measured according to ISO1133 at 230° C.; loads from 2.16 kg to 21.6 kg were used, to accommodatefor the wide range of melt viscosities observed.

[0047] The blow molding evaluations were done on a Battenfeld Fischermachine equipped with a screw having 60 mm diameter and 20 L/D length.Barrel and die temperatures were set in a way that the melt temperaturemeasured with a hand probe is 230 +/−2° C. With the screw turning at aconstant speed of 31 rpm, the parison is extruded through a circular diewith an outer diameter of 23.8 mm and a core pin diameter of 18.4 mm.During its descent from the die towards the floor, the advance of theparison is measured in the following way: the parison is cut at the dieexit and this defines the time as zero, then the time is recorded whenthe lowest point of the parison has moved by 1 dm, repeatedly up to 12dm. Four such measurements are made and averaged. The average times areused to extract the sag length, which is defined as the length at whichthe parison speed is twice its speed measured between 1 and 2 dm. Thesag length can be obtained either by direct inspection of the data, orby fitting an appropriate equation through the raw data and calculatingthis length from the derivative of the fitted equation. A higher valueof the sag length indicates that the material has less tendency to sagunder its own weight, which translates into better suitability for theproduction of long parts by the blow molding process. This is especiallyimportant for blow molding techniques that involve parison manipulationand/or sequential extrusion of different materials.

[0048] Being a measurement of viscosity, the melt flow rate wassometimes taken as a first screening indicator of the behavior of amaterial in the blow molding process. There is a strong correlationbetween low MFR values (high viscosity) and high sag length values inblow molding. Hence, the blow molding evaluation was not done for allcases, especially at the early stages and for the materials which didnot seem promising based on the MFR value.

[0049] Additional criteria were used to qualify the blow moldingbehavior of the resins. In particular the parison and the finished partwere visually observed to detect the presence of melt fracture (sharkskin) or of inhomogeneities, undispersed material, gel-like particles orlumps. Emission of smoke or volatile compounds leading to objectionableodors were also monitored during the blow molding process.

Description of Ingredients

[0050] Materials used in the Examples set forth below are as follows,identified by the respective trademarks and trade designations:

[0051] TEEE 1: HYTREL 5556, a thermoplastic polyester elastomer fromE.I. du Pont de Nemours having a Shore D Hardness of 55 and a melt flowrate of 7.5 dg/min at 220° C. under 2.16 kg load.

[0052] TEEE 2: HYTREL 5586, a thermoplastic polyester elastomer fromE.I. du Pont de Nemours having a Shore D Hardness of 55 and a melt flowrate of 4.5 dg/min at 220° C. under 2.16 kg load.

[0053] TEEE 3: HYTREL 3078, a thermoplastic polyester elastomer fromE.I. du Pont de Nemours having a Shore D Hardness of 30 and a melt flowrate of 5 dg/min at 190° C. under 2.16 kg load.

[0054] TEEE 4: HYTREL HTR4275 BK316, a thermoplastic polyester elastomerfrom E.I. du Pont de Nemours having a Shore D Hardness of 55 and a meltflow rate of 1.5 dg/min at 230° C. under 5 kg load. This particularresin grade is widely used and considered as a benchmark in the blowmolding of technical components in thermoplastic polyester elastomers.

[0055] Terpolymer 1: a terpolymer of ethylene/28% n-butyl acrylate/5.2%glycidyl methacrylate having a melt flow rate of 12 dg/min at 190° C.under 2.16 kg load, commercially available as ELVALOY AM from E.I. duPont de Nemours.

[0056] Terpolymer 2: a terpolymer of ethylene/25% methyl acrylate/6.5%glycidyl methacrylate having a melt flow rate of 6 dg/min at 190° C.under 2.16 kg load, commercially available as LOTADER AX8900 fromAtofina.

[0057] Terpolymer 3: a terpolymer of ethylene/30% ethyl acrylate/2%maleic anhydride methacrylate having a melt flow rate of 7 dg/min at190° C. under 2.16 kg load, commercially available as LOTADER 4700 fromAtofina.

[0058] Rubber 1: an acrylate terpolymer having a Shore A hardness of 53,commercially available as SUNIGUM P7395 from Goodyear Chemical.

[0059] Rubber 2: a butyl acrylate/PMMA core-shell modifier, commerciallyavailable as PARALOID) EXL 2314 from Rohm & Haas Co.

[0060] Black masterbatch: a masterbatch of carbon black in polyetherester elastomer, commercially available as HYTREL 41CB from E.I. du Pontde Nemours.

Screening Experiments

[0061] Compositions were prepared using eight different epoxy compoundsincorporated one by one in TEEE1 (A1), in presence of calcium oxide andzinc stearate. It appeared clearly that the Terpolymers 1 and 2 weremost efficient to increase the viscosity of the composition, resultingin MFR values as low as 0.1 dg/min at 230° C. under 2.16 kg load. Incontrast, epoxy bisphenol condensation products, such as EPON 1004F fromShell, yielded compositions with a viscosity equal or close to theviscosity of the initial TEEE 1 (above 20 dg/min at 230° C./2.16 kg).Intermediate results were obtained with a polyglycidyl ether ofortho-cresol novolac, commercially available as EPON 164 from ShellChemicals, and with a mixture of 70-82% terephthalic aciddiglycidylester and 18-30% trimellitic acid triglycidylester,commercially available as ARALDITE PT910 from Ciba Specialty Chemicals.

[0062] A second series of screening experiments was done, where thevariables were the concentrations of Terpolymer 2 (4-15%), Terpolymer 3(0-15%), calcium oxide (0-1%), black masterbatch (3-10%), and TEEE 2(59-93%, adjusted to a total of 100% for each composition). It was foundthat the dominant factor controlling viscosity is the concentration ofthe Terpolymer 2: addition of 15% Terpolymer 2 increases the viscosityso much that it becomes essentially impossible to process the resultingmaterial, whereas addition of 4% Terpolymer 2 increases the viscosity toMFR values comprised between 0.8 and 5.3 dg/min at 230° C. under 5 kgload. These experiments also demonstrated clearly that, all otherparameters being equal, the presence of calcium oxide increases theviscosity, whereas the amount of black masterbatch has no significantinfluence on viscosity.

COMPARATIVE EXAMPLES 1 TO 5

[0063] The compositions of Comparative Examples 2 to 5 in Table 1 wereprepared by extrusion as described above; in addition to the ingredientslisted there, they each also contained 1% calcium oxide (component E),2% black masterbatch and 1.9% stabilisers. Blow molding evaluation ofComparative Examples 1 to 5 was done on the Battenfeld Fischer machineusing the above procedure, and the sag length was measured by readingdirectly from the raw data.

[0064] It is found that the sag length is more sensitive to theconcentration of Terpolymer 2 than to that of Terpolymer 3. Furthermore,melt fracture is clearly visible when the concentration of Terpolymer 2is 10%. Compared to the behaviour of the benchmark material TEEE 4, theComparative Examples 2 to 4 show some improvement of sag length, whereasComparative Example 5 which has much longer sag length is hampered by asevere melt fracture, leading to unacceptable aspect of finished parts.TABLE 1 Component Ingredients CE 1 CE 2 CE 3 CE 4 CE 5 Al TEEE 2 [%]87.1 85.1 85.1 85.1 TEEE 4 [%] 100 B Terpolymer 2 [%] — 6 6 8 10 CTerpolymer 3 [%] — 2 4 2 Ratio B/A [%] 6.9 7.1 9.4 11.8 Sag length [dm]4.5 5 6 7 10.5 Parison aspect Good Good Good Good Melt fracture

EXAMPLES 1 TO 6 AND COMPARATIVE EXAMPLES 6 AND 7

[0065] The compositions of Examples 1 to 6 and Comparative Examples 6and 7 in Table 2 were prepared by extrusion as described above; inaddition to the ingredients listed there, they also each contained 1%calcium oxide (component E), 2% black masterbatch, 0.4% zinc stearateand 1.4% stabilizers. Blow molding evaluation was done on the BattenfeldFischer machine, and the sag length was calculated from the equationfitted through the raw data. TABLE 2 Component Ingredient Ex 1 Ex 2 Ex 3Ex 4 Ex 5 Ex 6 CE 6 CE 7 A1 TEEE 1 [%] 49.2 49.2 57.2 65.2 A1 TEEE 2 [%]57.2 57.2 75.2 65.2 A2 TEEE 3 [%] 10 10 10 10 10 10 10 20 B Terpolymer 2[%] 8 8 8 10 8 8 10 10 C Terpolymer 3 [%] 8 8 10 D Rubber 1 [%] 20 20 20D Rubber 2 [%] 20 20 Ratio B/A [%] 13.5 13.5 11.9 13.3 11.9 11.9 11.711.7 Sag length [dm] 42 21 19 12 22 33 (a) (a)

[0066] No melt fracture was observed in any of the Examples 1 to 6. Thisshows that presence of the softer components TEEE 3 and/or rubberstrongly reduces the tendency for the parison to show melt fracture.Very high sag length values are found with a fair parison aspect; somelumps or gel-like particles were observed with all examples, and somesmoke was evolved with examples 1, 2, 3 and 5, but these defects areminor and cosmetic rather than functional.

[0067] Comparative Examples 6 and 7 show that although Terpolymer 3 andrubber are each optional, there must be at least one of these in thecomposition.

EXAMPLES 7 TO 25 AND COMPARATIVE EXAMPLE 8

[0068] A design of experiments was done, where the compositions are asdescribed in Table 3. All compositions in this Table also contained 2%black masterbatch, 1% calcium oxide (component E), 0.4% zinc stearateand 1.4% stabilizers.

[0069] All examples in Table 3 have high viscosity, as shown by the MFRvalues measured at 230° C. under 21.6 kg load. Comparative Example 8shows that when the amount of Terolymer 2 is higher than 15% of theamount of blend A, then the composition becomes too viscous to beextruded. This finding is in agreement, and indeed more strict, than theobservation done with the second series of screening experiments, wherecompositions using Terpolymer 2 at 15% of the total composition (i.e. 18to 25% relative to TEEE 2) were too viscous to be processed. It can alsobe seen that all Examples comply with this upper limit of 15% componentB relative to the blend A.

[0070] The Examples 7 to 25 also all show much improved sag lengthrelative to the benchmark TEEE 4 (Comparative Example 1, Table 1).Indeed some compositions of Table 3 have extremely high melt strength,with essentially no sagging over the measurement height of 1.2 m (almostno curvature of the parison length versus time graph, sag lengthcalculated as high as 50 dm).

[0071] The surface aspect of the parts was estimated globally, based onpresence of melt fracture, lumps, pits/craters and other aspect defects.The best surface aspect with no visible surface defects, which wasobtained with the benchmark material TEEE 4 (Comparative Example 1),reached the score of 10 on this scale. Materials within Examples 7 to 25exhibit surface aspect of parison and finished parts ranging from ratherpoor (e.g. Ex. 19) to very good (e.g. Ex. 7).

[0072] The Examples have been given to illustrate but not to limit theinvention. Depending on the desired pattern of characteristics, personsskilled in the art will be able to select from the range of possiblecompositions exemplified here the optimal combination between processingbehavior and aspect of the parison and finished parts. TABLE 3 Com-ponent Ingredient Ex 7 Ex 8 Ex 9 Ex 10 Ex 11 Ex 12 Ex 13 Ex 14 Ex 15 Ex16 Ex 17 A1 TEEE 1 [%] 74.2 59.2 76.2 72.2 69.2 65.2 65.2 69.2 63.2 67.275.2 A2 TEEE 3 [%] 4 10 7 7 4 4 10 10 8 8 4 B Terpolymer 2 [%] 6 8 6 8 68 10 8 8 8 8 C Terpolymer 3 [%] 6 8 6 8 6 8 10 8 8 8 8 D Rubber 1 [%] 1010 8 D Rubber 2 [%] 5 10 4 Ratio B/A [%] 7.7 11.6 7.2 10.1 8.2 11.6 13.310.1 11.2 10.6 10.1 Sag length [dm] 8 16 10 26 11 50 31 19 17 30 28Aspect (a) 9 8 8 6 7 7 7 7 8 4 5 MFR (b) [dg/mm] 12.1 3.3 6.1 1.2 4.61.9 0.3 0.9 2.1 0.4 0.8 Com- ponent Ingredient Ex 18 Ex 19 Ex 20 Ex 21Ex 22 Ex 23 Ex 24 Ex 25 CE 8 A1 TEEE 1 [%] 65.6 73.2 69.1 79.2 63.2 71.276 68.2 61.2 A2 TEEE 3 [%] 5.6 10 3.6 4 10 7 3.2 9 4 B Terpolymer 2 [%]8 6 9 6 6 6 8 9 10 C Terpolymer 3 [%] 8 6 9 6 6 6 8 9 10 D Rubber 1 [%]4.5 5 10 D Rubber 2 [%] 8 10 Ratio B/A [%] 11.2 7.2 12.4 7.2 8.2 7.710.1 11.7 15.3 Sag length [dm] 41 10 34 11 22 11 25 20 (c) Aspect (a) 61 7 5 7 8 7 2 MFR (b) [dg/mm] 0.3 5.5 0.3 4.8 1.9 6.3 0.8 0.5

1. A moldable resin composition comprising: (A) a blend of twocopolyester elastomers (A1) and (A2): (A1) with a hardness in the range45-72 Shore D, in an amount 75-97 wt. % of the blend, and (A2) with ahardness in the range 25-40 Shore D, in an amount 3-25 wt. % of theblend; (B) a copolymer comprising from 94 to 50 wt. % of ethylene, from5 to 35 wt. % of at least one alkyl or cycloalkyl acrylate ormethacrylate, in which the alkyl or cycloalkyl group has from 2 to 10carbon atoms, and from 1 to 15 wt. % of at least one unsaturatedepoxide; at least one of (C) and (D) where: (C) is a copolymercomprising from 88 to 60 wt. % of ethylene, from 11.5 to 40 wt. % of atleast one alkyl or cycloalkyl acrylate or methacrylate, in which thealkyl or cycloalkyl group has from 2 to 10 carbon atoms, and from 0.5 to6 wt. % of at least one anhydride of an unsaturated dicarboxylic acid;(D) is at least one rubbery polymer that can be dispersed finely intothe composition by extrusion; (E) a calcium compound capable of reactingwith acid end-groups of the polyether ester resins of blend (A); and (F)one or more optional additives; wherein the resin blend (A) is presentin an amount of 60-90 wt. % of the composition; copolymer (B) is presentin an amount of 6-15 wt. % of the blend A; copolymer (C) when present isin an amount up to 20 wt. % of the composition, and component (D) whenpresent is in an amount up to 20 wt. % of the composition, providing thesum of (C) and (D) is at least 2 wt. % of the composition; the calciumcompound (E) is in an amount such as to provide up to 2 wt. % elementalcalcium in the composition; and the optional additive(s) (F) whenpresent is/are in an amount up to 20 wt. % of the composition.
 2. Thecomposition of claim 1 wherein at least one of the copolyesterelastomers (A1) and (A2) is a copolyetherester consisting essentially ofa multiplicity of recurring long chain ester units and short chain esterunits joined head-to-tail through ester linkages, said long chain esterunits being represented by the formula

and said short chain ester units being represented by the formula

where G is a divalent radical remaining after removal of terminalhydroxyl groups from a poly(alkylene oxide) glycol having a molecularweight of about 400-6000 and a carbon-to-oxygen ratio of about 2.0-4.3;R is a divalent radical remaining after removal of carboxyl groups froma dicarboxylic acid having a molecular weight less than about 300 and Dis a divalent radical remaining after removal of hydroxyl groups from adiol having a molecular weight less than about 250; provided said shortchain ester units amount to about 15-95% by weight of saidcopolyetherester.
 3. The composition of claim 1, wherein at least one ofthe copolyester elastomers (A1) and (A2) is a copolyester ester.
 4. Thecomposition of claim 1, wherein blend (A) contains copolyester elastomer(A1) in an amount 84-94 wt. % and copolyester elastomer (A2) in anamount 6-16 wt. % of the blend.
 5. The composition of claim 1, whereincopolymer (B) and copolymer (C), when present, comprise alkyl acrylatesand methacrylates selected from: methyl methacrylate, ethyl acrylate,n-butyl acrylate, isobutyl acrylate and 2-ethyl-hexyl acrylate.
 6. Thecomposition of claim 1, wherein copolymer (B) comprises unsaturatedepoxides selected from aliphatic glycidyl esters and ethers, andalicylic glycidyl esters and ethers.
 7. The composition or claim 1,wherein copolymer (C) comprises anhydrides of an unsaturateddicarboxylic acid selected from maleic anhydride, itaconic anhydride,citraconic anhydride and tetrahydrophthalic anhydride.
 8. Thecomposition of claim 1, wherein the rubbery polymer (D) is at least oneof an acrylate terpolymer rubber and a butyl-acrylate/PMMA multiphasecomposite interpolymer.
 9. The composition of claim 1, wherein thecalcium compound (E) is calcium oxide or calcium hydroxide in an amountup to 2 wt. % of elemental calcium.
 10. The composition of claim 1,wherein the optional additives (F) include a compound capable ofaccelerating the reaction between the epoxy groups present in thecopolymer (B) and the acid end-groups of the copolyester elastomers (A1)and (A2).
 11. A process for forming a molded article, comprising thesteps of heating the composition of claim 1 above its meltingtemperature, forming the composition into a desired shape, and allowingthe composition to cool for form a molded article.
 12. A process forblow-molding an article, comprising the steps of providing a compositionaccording to claim 1, forming a parison comprising said composition,inserting the parison into a mold, blowing a gas through the parison toform a blow molded article
 13. A shaped article that includes thecomposition of claim 1.